Methylol derivatives of halo-cyanoacetamides and their application to cellulosic materials



United States Patent 3,403,174 METHYLOL DERIVATIVES OF HALO-CYANO- ACETAMIDES AND THEIR APPLICATION TO CELLULOSIC MATERIALS Leon H. Chance and Ethel K. Leonard, New Orleans, La.,

assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Original application Mar. 9, 1965, Ser. No. 438,430, new Patent No. 3,350,164, dated Oct. 31, 1967. Divided and this application June 1, 1967, Ser. No.

2 Claims. (Cl. 260465.4)

ABSTRACT OF THE DISCLOSURE The N-methylol derivatives of dibromocyanoacetamide and dichlorocyanoacetamide were prepared by reacting said compounds in aqueous solutions of pH about from 7.0 to 9.0 with formaldehyde in the mole ratio of the selected amide to formaldehyde of about from 1:1 to 1:3, at room temperatures to yield compounds useful as cellulosic textile finishing agents.

This application is a division of application bearing Ser. No. 438,430; filed Mar. 9, 1965, which has since matured into Patent No. 3,350,164, granted Oct. 31, 1967.

A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to halogen containing methylolamides and polymeric derivatives thereof; to methods for preparing the said halogen containing methylolarnides and the said polymeric derivatives thereof; and to a process for utilizing these compounds. More specifically, this invention relates to halo-cyanoacetamides, to new methylol derivaties prepared from halo-cyanoacetamides, and methods for preparing and using these as finishes for cellulosic textiles.

One object of this invention is the preparation of methyloldihalocyanoacetamides from dihalocyanoacetamides.

A second object ofthis invention is the preparation of finishing agents for cellulosic textiles.

The compounds of this invention are particularly useful as finishing agents for cellulosic textiles in that when these compounds are applied to cellulosic textiles the said textiles are rendered wrinkle-resistant, rot-resistant, flameresistant, and the finish is resistant to both acid and base hydrolysis.

The equations applicable to the preparation of compounds of our inventionwherein X is a halogen, including fluorine, chlorine, bromine, and iodine-are presented here to facilitate the teaching of the art of our invention.

dihaloeyanoacetamide dimethyloldihaloeyanoacetarnide Cir "ice

The prior art teaches that acetamide reacts with formaldehyde to form the dimethylol derivative (ref. Vail, S.L., et al., Amer. Dyestuff Reptr. 50, 437 (1961), and that said derivative produces wrinkle resistance when applied to cotton. However, the Wrinkle resistance and nitrogen and formaldehyde content of cotton fabric treated with dimethylol acetamide are greatly reduced by hydrolysis. The methylol derivatives of this invention, i.e., the methylol derivatives of dihalocyanoacetamides, offer a definite advantage over the prior art in that the finish on the cotton is much more resistant to removal by hydrolysis, and hence is more stable to hydrolytic conditions encountered in laundering. This hydrolytic stability is due to the presence of the strongly electron-Withdrawing groups-Cl, Br, and CEN. A further advantage over the prior art is a significant degree of flame resistance imparted to the cotton due to the presence of the halogens.

The methylol derivatives of dichlorocyanoacetamide and dibromocyanoacetamide of this invention can be prepared by bringing into reactive combination the amide and formaldehyde in aqueous alkaline solution. The reaction takes place at room temperatures about from 25 to 45 C. In general, the methylolation reaction is carried out in mole ratios of amide to formaldehyde of about from 1:1 to 1:3. The reaction is carried out in aqueous solutions adjusted to pH about from 7.0 to 9.0 with an alkali metal hydroxide, such as sodium hydroxide. The reaction usually reaches equilibrium in about from 18 to 24 hours, and probably contains a mixture of the monomethylol and dimethylol derivatives. The methylolamides are not isolated from the solutions before application to cellulosic textiles. To minimize polymerization, the solutions are preferably stored in a refrigerator until ready to be used.

During the reaction of formaldehyde with dichlorocyanoacetamide and dibromocyanoacetamide, small amounts of white solid polymer precipitated. The polymers contain nitrogen and the corresponding halogen.

Cellulosic textile fiber, yarns, and fabrics can be made wrinkle resistant in accordance with this invention. The process consists essentially of impregnating the textile materials with an aqueous solution of the methylol derivatives, and curing the impregnated materials at tempera tures conventionally used for curing cellulosic textiles.

' The time and temperature required for curing the impregnatecl textile is dependent on the particular compound and upon the weight of fabric being treated. The temperature can range about from 100 to 160 C. For the bromine containing compound, at temperatures above about 140 C., the fabric becomes degraded due to the low decomposition point of the resin on the cellulosic mate rial. This resin would be useful in those cases where resins with low decomposition points are desirable. The curing time of the material on the fabric can vary about from 1 to 30 minutes. The rapid cures are accomplished at the higher temperatures.

Simultaneous polymerization within and crosslinking of the cellulose molecules of the fibers provided by this invention are produced in the presence of an acid catalyst. Catalysts suitable for the reaction are those conventionally used in applying methylol amides to cellulosic materials. These catalysts are Lewis acids and protonic acids, and include latent acid catalysts, such as magnesium chloride, zinc nitrate, zinc fluoborate, and amine hydrochlorides.

When a cotton textile is being treated, it is advantageous to pass it through the impregnating liquor to thoroughly wet it and remove excess liquor by passing the wetted textile through squeeze rolls. It is also advantageous to dry the textile at a temperature of about from 60 to 100 C. before curing. Preferred drying is carried out at about from to C. for about three to five minutes, while preferred curing is carried out at about from to C. for about from three to five minutes, the longer periods of time being employed with the lower temperatures.

The degree of flame resistance, crease resistance, and rot resistance can be varied by varying the amount of polymer and crosslinking put into the textile.

LIMITS AND PREFERRED RANGE For preparation of the methylol derivatives, the limits TABLE I Wnnkl' e Sample I Catalyst, Solution, Curing Add-on, Recovery Number Type Catalyst Percent pH Temp., C. Percent Angles (Warp and Fill), Degrees 1 Zn(NOa)2:6H2O 1.0 6. 45 145 3.7 235 Zn(NO3)2:6H2O 1.0 6. 45 150 4.4 241 ZI1(BF4)2 1.6 4.0 140 5.1 252 ZI1(BF4)2 1.6 4.0 150 6.3 260 Amine hydrochloride... 0. 7 6. 5 140 6. 3 233 do 0.7 6. 5 150 7. 7 268 MgC1z:6H2O 3. 0 6. 4 140 5. 6 267 MgClzzfiHzO. 3.0 6.4 150 5.3 282 1 Control had wrinkle recovery angle (warp and till) of 188.

of reaction temperature are about from 0 to 45 C. The preferred range is about from to C. The limits of reaction time are about from one hour to 24 hours. The preferred range is about from 18 to 24 hours. The limits of mole ratio of halocyanoacetamide to formaldehyde are about from 1:1 to 1:3. The preferred ratio is 1:2.

For the application of the methylol derivatives to cotton, the limits of drying time and temperature are about from one to ten minutes at about from 50 to 100 C. The preferred range is about from three to five minutes at about from 85 to 100 C. The limits of curing time and temperature are about from one to ten minutes at about from 100 to 160 C. The preferred range is about from three to five minutes at about from 135 to 145 C.

The following examples illustrate the methods of carry ing out the invention; however, the examples are not meant to limit the invention in any manner whatever. The fabrics treated by process of this invention as well as the controls were tested by the standard methods recommended by the American Society for Testing Materials, Philadelphia, Pa., Committee D-l3. Breaking strength was determined by the one-inch strip method, ASTM designation D39-59; tearing strength by the Elmendorf method, ASTM designation D1295-60T; wrinkle recovery by the Monsanto method, ASTM designation D1424-59g rot resistance by the soil-burial method, ASTM designation D684- 54; and flame resistance by the standard vertical method, Federal Specification CCC-T-l9lb. All percentages and parts are by weight.

Example 1 96.8 parts of dibromocyanoacetamide, 100 parts of 36.3% aqueous formaldehyde, and 201.4 parts of water were mixed in a flask. This was a mole ratio of dibromocyanoacetamide to formaldehyde of 1:2. To the stirred mixture was added dropwise 4.3 parts of 12.5% aqueous sodium hydroxide. During the addition of the sodium hydroxide, the temperature rose spontaneously to 50 C. The temperature was not allowed to go above 50 C. by external cooling. The pH of the solution at the end of the sodium hydroxide addition was 9.6. The solution was stored in a refrigerator overnight. A small amount of white precipitate formed (2.6 parts) which was filtered and washed with acetone. The white solid was a polymer containing 9.52% nitrogen and 52.98% bromine.

The clear filtrate had changed to a pH of 6.8 on standing overnight. The solution contained theoretically about 29% of the formaldehyde derivative of dibromocyanoacetamide. The solution was diluted with water to 14% and used to treat samples of cotton printcloth. The solu- All of the samples cured at 150 C. were discolored, indicating that 140-145 C. is a more desirable temperature. Also, samples treated at 150 had greater strength losses than those treated at 140-145 C. All of the samples exhibited some flame resistance.

Example 2 A solution containing 20% of the formaldehyde derivative of dibromocyanoacetamide was prepared as in Example 1. To the solution was added 1.2 parts of per 100 parts of solution. The solution was padded on to a sample of cotton printcloth as in Example 1. The fabric was dried for five minutes at C. and cured at 140 C. for five minutes. The fabric had a resin add-on of 8.5%. Data on wrinkle recovery, strength, and elemental analysis before and after laundering and hydrolysis are shown in Table II.

TABLE II Original (0.) 1 (b) 1 l 1 Wrinkle recovery angles, den-ces 269 256 274 268 270 Breaking strength (war lbs 27. 6 30. 6 Tearing strength (War gms 445 380 Nitrogen, percent- 0.86 0.75 0 68 0 83 Bromine, percent". 4. 86 3.87 2 74 3 93 Formaldehyde, percent... 0.66 0. 86 0 71 0 79 (a) After ten washes; (b) After acid hydrolysis at pH 4; (c) After base hydrolysis at pH 10; (d) After stripping with urea-phosphoric acid.

Example 3 A solution was prepared as in Example 1 except the mole ratio of dibromocyanoacetamide to formaldehyde was 1:3. The solution contained 48.4 parts of dibromocyanoacetamide, 50.6 parts of 36.3% aqueous formaldehyde, 52.1 parts of water, and 2.1 parts of 12.5% sodium hydroxide. T0 the solution was added 1.2 grams of per grams of solution. The solution was padded on to 8.5 ounce sateen cotton fabric as in Example 1. The

fabric was dried five minutes at 100 C. and cured for ten minutes at 140 C. The fabric had a resin add-on of 9.7%, a wrinkle-recovery angle of 238, and a char length of 5.1 inches by the standard vertical flame test.

were dried for five minutes at 85 C., and cured for five minutes at 160 C., washed in hot water, and dried. Resin add-on, strength, and wrinkle-recovery angles are shown in Table III.

Example 4 A solution was prepared as in Example 1 except the mole ratio of dibromocyanoacetamide to formaldehyde was 1:1. The solution was diluted with water to a concentration of 27% based on the theoretical yield of a monomethylol derivative. To the solution was added 1.2 parts of Zn-(N-O -6H O per 100 parts of solution.

The solution was applied to cotton printcloth as in Example l, dried five minutes at 100 C., and cured five minutes at 140 C. The fabric had a resin add-on of 8.7%, and a wrinkle-recovery angle of 235. It also had significant flame-resistance. The wrinkle recovery indicated crosslinking and hence the presence of some of the dimthylol derivative in the solution.

Example 5 A solution was prepared as in Example 1 with the following quantities: 193:6 parts of dibromocyanoacetamide, 198.3 parts of 36.3% aqueous formaldehyde, 212.1 parts water, and 5.5 parts of 12.5% aqueous sodium hydroxide. This was a mole ratio of dibromocyanoacetamide to formaldehyde of 1:3. 1.2 parts of Zn(NO -6H O per 100 parts of solution was used as a catalyst. The solution was padded on to samples of cotton printcloth as in Example 1. The samples were dried for five minutes at 100 C. and cured for eight minutes at 140 C. The fabric had a resin add-on of 12.8%, and a wrinkle-recovery angle of 285 (warp and filling). The breaking strength of the treated fabric was 26.6 lbs. The fabric was subjected to soil burial tests to determine rot resistance. After 18 weeks in soil burial beds, the samples had a breaking strength of 18.3 lbs. Since this was a strength retention of 69%, the fabric exhibited considerable rot resistance.

Example 6 30.6 parts of dichlorocyanoacetamide, 33.0 parts of 36.3% aqueous formaldehyde, and 131.4 parts of water were mixed in a flask. This was a mole ratio of amide to formaldehyde of 1:2. While stirring, five parts of 12.5% aqueous sodium hydroxide were added dropwise over a period of about ten minutes. The temperature of the reaction rose spontaneously to 49 C. in about three minutes, but was cooled to 35 C. by external cooling and maintained at this temperature during the remainder of the addition time. The pH was 9.9. After standing for one hour at room temperature, the pH had changed to 6.85. It was made to a pH 8.5 by the addition of more sodium hydroxide. After 1.5 hours more, the pH had changed to 6.75. It was made to pH 8.5 again and allowed to stand overnight at C. Assuming a theoretical yield of the dimethylol derivative, the solution was diluted with water to a solution. The solution was divided into three parts and MgCl -6H O added as a catalyst in concentrations indicated in Table III. The solutions were padded on to samples of cotton printcloth as in Example 1. They The untreated fabric had a wrinkle recovery angle of 188. The data shows that there was an improvement in wrinkle recovery, although it was not as great as that obtained with dibromocyanoacetamide. There was a small degree of flame resistance. The dibromocyanoacetamide was more effective as a flame retardant.

Example 7 A solution was prepared as in Example 6. The solution was divided into two parts and labeled Solution I and Solution II. Solution I was diluted with water to a concentration of about 10% based on the dimethylol derivative. Zn(NO -6H O was added as a catalyst to provide a concentration of four parts per parts of solution. Solution II was diluted with water to a concentration of about 15% based on the dimethylol derivative. MgCl -6H O was added as a catalyst to provide a concentration of four parts per 100 parts of solution. Samples of cotton pn'ntcloth were padded with the solutions as in Example 1. The samples were dried for five minutes at 85 C. and cured for five minutes at C., washed, and dried. The fabric treated with Solution I had a wrinkle-recovery angle of 268 (warp and filling), and the fabric treated with Solution II, 229 (warp and filling).

Example 8 The reaction of formaldehyde with dichlorocyanoacetamide was carried out as in Example 6. When the reaction was complete a small amount of white polymer had precipitated. The polymer contained 12.2% nitrogen, 30.8% chlorine, and 12.1% formaldehyde.

We claim:

1. The methylol derivative of dibromocyanoacetamide produced by reacting dibromocyanoacetamide with formaldehyde in the mole ratio of about from 1:1 to 1:3, respectively, in an aqueous solution having a pH of about from 7.0 to 9.0 at a temperature of about from 25 C. to 45 C.

2. The methylol derivative of dichlorocyanoacetamide produced by reacting dichlorocyanoacetamide with formaldehyde in the mole ratio of about from 1:1 to 1:3, respectively, in an aqueous solution having a pH of about from 7.0 to 9.0 at a temperature of about from 25 C. to 45 C.

References Cited UNITED STATES PATENTS 6/1963 Rosenblatt 260-465.4 XR

OTHER REFERENCES Vail et al., American Dyestutf Reporter, vol. 50, 1961. pp. 437-440 and 464.

JOSEPH P. BRUST, Primary Examiner. 

